alpha-substituted acrylic acids and esters and polymers thereof



Patented Aug. 7, 1951 a.-SUBSTITUTED ACRYLIC ACIDS AND ESTERS AND POLYMERS THEREOF Joseph B. Dickey and ll-Ia'rry W. Coover, J r., Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey N Drawing. Application December 9, 1949, Serial No. 132,217

Claims. (Cl. 26077.5)

This invention relates to a-(alkoxycarbon amido)-acrylic acids, esters and homopolymers and copolymers thereof. 4

Various a-substituted acrylic acids and esters, their polymers and copolymers, have "previously been described in the patent literature and elsewhere. However, to the best of our knowledge, the a-(alkoxycarbonamido) substituted compounds of the invention have not previously been described.

The compounds of the invention have the following general structure:

have the structure:

wherein R and R1 are both alkyl groups preferably from 1 to 4 carbon atoms but which may be diiferent depending upon the starting material and the reactant used in esterification.

The a-(alkoxycarbonamido)-acrylic acids and esters readily homopolymerize and copolymerize with one or more monomers under the usual conditions. The usual catalyst, such-as hydrogen peroxide, benzoyl peroxide, potassium persuliate,

or ultraviolet light, and so forth, are used, and certain so-called activating agents, such as sodium bisulfite, may be used in connection with the usual catalyst.

The homopolymers are soluble in many common solvents such as acetone and alcohol. Further, the homopolymers exhibit many valuable properties such as high clarity, hardness, toughness, high heat distortion temperatures, and so forth. Certain of these properties such as hardness and heat distortion temperatures depend on the length of the alkyl chains. For example, the

homopolymer of methyl a (methoxycarbonamido) -acrylate is harder and has a higher heat distortion point than the homopolymer of propyla- (propoxycarbonamido) -acrylate.

By the copolymerization of these new mono mers with other monomers, polymers having many properties can be prepared. For example,

copolymerizing by weight of methyla (methoxycarbonamido)-acrylate with acrylonitrile, a polymer is obtained which has a softening point above 200 C. and can be spun into fibers which have excellent dyeing properties.

Other monomers containing a polymerizable CI-Iz=C or CI-I=C group which can be polymerized with the monomers of general formulas above include vinyl halides, acrylates, the amethacrylates, fumarates, maleates, vinyl esters, alkyl alkenyl ketones, a-acyloxy-alkenyl nitriles, alkenyl nitriles, and hydrocarbons containing conjugated olefinic unsaturation, such as styrene.

More specifically, monomers which can be polymerized with the compounds of the invention are those set forth in the Magoilin et a1. U. S. patent application Serial No. 773,736, filed September 12, 1947, now U. S. Patent 2,487,885. Copolymers with acrylonitriles, vinyl esters, styrenes, and vinyl halides are especially valuable. The acrylic acids and esters of the invention may be prepared, for example, from the ma bis- (alkoxycarbonamido) -propionic acids as i1- lustrated by the following reaction:

CHs-GCOOH HOAC (NH-O0 OR):

capo-coon Esterlfication capo-coon NH-oooa NH-OOOR The a,a bis (alkoxycarbonamido) propionic acids may be prepared by the reaction of alkyl carbamates with pyruvic acid by the method of Kraft and Herbst, J. Org. Chem. 10, 496 (1945). Suitable alkyl carbamates are, for example, methyl-, ethyl-, propyl-, isopropyl-,nbutyl-, isobutyl-carbamates, etc.

According to the above reaction, the correspondin act-substituted propionic acid is heated with acetic acid to form the a-(alkoxycarbonamido)-acrylic acid which is then esterified by well-known methods, such as by treating the silver salt of the acrylic acid with an :alkyl halide or by saturating an alcoholic solution of the acrylic acid with dry hydrogen chloride. The esters are then purified by distillation under reduced pressure. J

The following examples give in detail. methods of preparation of the monomers, homopolymers and copolymers of our invention:

A solution of 54.8 grams of a,a-bis(ethoxycar- .bonamido)-propionic acid in cc. of glacial acetic acid was refluxed for 15 minutes. The acetic acid was removed by distillation at 20 NHzCOOEt mm., and; theurethane: was removed. at Lmm'; leaving the product as a viscous oil, soluble in ethanol and insoluble in hexane. The molecular weight of the acid as determined from its neutral equivalents was 158.

Example 2.-a-(Isopropozcycarbonamide) -acrylic acid CHBOCOOH CHaC-O-OH NH-C O O CH(CHa)z inshexanen The molecula Weight of. the acid'as determined. from its. neutral-equivalents was 171.

Example 3' Example4 Ten grams of a-isop-ropoxycarbonamido acrylic acidwas' dissolvedin 50 ml. of water and heated at60 C. for 6-8 hours. The acid"p o1ymerized*to give aviscous solution. Thepolymer can be pre cipitated by" the addition of acetone to give a hard} white polymer.

Example Two grams of a-methoxycarbonamido acrylic acid and 8 grams of acrylonitrile were added to 100 ml. of distilled water containing" 0".1" gram of ammonium persulf ate and 0.2 gram" of sodium bisulfitez. The reaction vessel was sealed from the outside air. and maintained at 35-40 C. for 6 hours. A fine white insoluble polymer was formed which wasfiltered ofi, well. washed" with waterg anddrie'd. The polymer. is soluble in dimethyl' formamide and. does not soften below 195C;

Example 6 Eight grams of a-ethoxycarbonamido; acrylic acid and 2.. gramsof; vinyl. acetate .-were-added .to 75.-ml.- of: distilled water containing 0.3;gramof hydrogen. peroxide. The'polymerization wascarri'ed'outby heating at 50 C. for 12 hours. A clearviscous solution resulted. Thepolymerrcan beeprecipitated by;the. additionof acetone. Hard, somewhat brittle. films. canbe-cast from thewater solution. ofthe: polymer; The polymer. has a softening point above 130 C.

Example? Z-partsofacrylamide and 3wparts of methacry'lic 3:016." were-dissolved in 100 ml. of distilled water containing 0.2Zgram of-ipotassium pers ulfate and 0.2 gram of sodium bisulfite. The polymerization was completed by heating at 40 C. for 8 hours. A clear, viscous solution resulted. The polymer 11 can be precipitated by the addition of acetone.

The -polymer hasa softening point above C.

Example 9 Ten;grams-.ofbutadiene and 3 grams of a-methoxycarbonamlddacrylic acid were polymerized in the presence of 40 grams of a 1.5% aqueous solution'of. potassium laurate as an emulsifying agent, 0.5 gram of hydrogen peroxide as a polymerization. modifier and 0.02 gram of ferrous sulfate. The polymerization was complete in about 24 hours,. and. the product .is a latex-like. dispersion resembling. material rubber latex.

The other a-substitutedacrylic acidsarepolymerized.inasimilarmanner.

Example 10.-'-Methyl a-(ethomycarbonamido) acrylate A solution of. 54.8.grams of. a,s.bis(ethoxycarbonamido)-propioni aeidin 150 cc. of glacial acetic acid was refluxed for 15.. minutes. The aceticqacid. wasv removed under .reduced pressure. A solution of 8.9 grams of sodium hydroxide. in 50 cc. of water was added with cooling, followed by a solution of 37.6" grams" of silver nitrate in 200 cc. of water. The silver salt thus formed was separated: by filtration; washed. twice? with. cold waterandtwicewith acetone. Thedry, p wdered silver.- sa'lt..was added witlnstirring to.20.0. grams of: methylriodide'; containing; about 0.05: gram. each of trinitrobenzene: and; hydroquinone; During the: addition, the; heat of'reaction causesthe methyl :iodide-.-to..-refi-ux. The-mixturewas: allowed to stir at room temperature. for half an hour, filtered, and the filtrate was distilled.

At 50-80/2 mm: 1512' grams of pale yellow oil was collectedx" Upon: redistillation': 818i grams? of methyliiadethoxycarbonamidh).-acrylate' was obtained as a clear liquid: B;...P 641-69512 mmz, N 1.4588, M. P..63 C. Analysis for nitrogen: calculated 8.1%, found 8.1%.

Example 11.Methyl a-(propomycarbonamidwacrylizte.

A solutionof "10 .0 grams of a-,u-bis--( npropoxy'- carbonamiddl-propionic acid in 50 cc; of acetic acid 'was-"refluxedfor' 10 minutes. The aceticacid was-removed under reduced"pressure. A-solution of""2.03 grams of sodiumliydioXidein 15"cc: of water"-was'= added; followed by" a solutionof 6 .15 rams offsilver-nitratein 30cc; of'water; The silver" saltwas separated" by filtration, washed witirwater; thenactone; The-dry, powderedsil ver salt 'was-ra'dded' to 30 cc; of methyliodid'e with stirring. The mixture was filtered and the filtrate distilled. At? 73'-1907l to 4 mm. 4.-15'gra-msof pale yellowoil was collected; This was redistilled to'give-2.10grams of methyla-in propoxycarbon amido') -acrylate; B.- P.' '70-71 /1mm:, Nb- '1A59l', M. P. 17-(2 Example. 12I-Ethy Z ar (isopropoxycarbonamido) acrylatei A solution of 15' grams" of a,w-bis-(isopropoxycarbonamidoi -propionic" acid in45 cc; of acetic saturated in' the=cold with'idry hydrogen chloride and allowedto stand at roomtemperature for'l ho r; T Ee QQ -Q .was"r mQvecratreduced-p sure; A solution of sodium ethoxide was added until the pH of the mixture was six. chloride was removed by filtration. The filtrate was distilled at reduced pressure to obtain the ethyl a- (isopropoxycarbonamido) -acrylate.

Example 13 Four grams of methyl a-(ethoxycarbonamido) acrylate was polymerized at 60 C. in an atmosphere of nitrogen using,0.l% acetyl peroxide as a catalyst. The product is a clear, hard polymer which can be molded.

Example 14 Eight grams of methyl a-(n-propoxycarbonamide) -acrylate was polymerized at 60 C. in an atmosphere of nitrogen using 0.1% acetyl peroxide as a catalyst. A clear, hard polymer which can be molded is formed.

Example 15 Five grams of ethyl, a-(isopropoxycarbonamido)-acrylate was polymerized by heating to 55 C. in an atmosphere of nitrogen. A clear, hard, moldable polymer is formed.

Example 16 Two grams of methyl a-(ethoxycarbonamido) acrylate and 8 grams of methyl methacrylate were copolymerized at 60 C. in an atmosphere of nitrogen using 0.1% acetyl peroxide as a catalyst. The product is a clear, hard, moldable polymer.

Example 18 Eight grams of styrene and 2 grams of methyl a-(n-propoxycarbonamido) -acrylate were copolymerized at 60 C. in a nitrogen atmosphere using 0.1% acetyl peroxide as a catalyst. A clear, hard polymer which can be molded is formed.

Example 19 Six grams of vinyl acetate and 1 gram of ethyl a-(isopropoxycarbonamido)-acrylate were copolymerized at 60 C. in an atmosphere of nitrogen using 1.0% benzoyl peroxide as a catalyst. A clear, hard, moldable polymer is obtained.

Example 20 Five grams of acrylonitrile, 1.0 gram of methyl a-(ethoxycarbonamido) -acrylate, 0.055 gram of ammonium persulfate and 0.1 gram sodium bisulfite were placed in 45 cc. of distilled water. The polymerization began immediately and was complete after several hours at 50 C. The white polymer was filtered, washed and dried. The polymer is soluble in dimethylformamide and in dimethylacetamide. Fibers having good properties can be spun from this type of copolymer.

Example 21 Two grams of methyl e-(ethoxycarbonamido) acrylate, '7 grams of vinyl chloride, 1 gram of soap, 0.05 gram of ammonium persulfate and 0.1 gram of ammonium bisulfite were added to 35 cc. of water in a pressure bottle. After 24 hours at 60 C., acetic acid was added and the white polymer was filtered, washed and dried. The product can be mo d d.

Sodium The above examples provide copolymers from mixtures of various proportions of the monomers of the invention with other monomers. In general, we can obtain valuable copolymers by polymerization of mixtures containing from 595% by weight of our monomers and 95-5% of other monomer or monomers by methods of the examples. However, for our purposes we prefer the range 550% by weight.

We claim:

1'. 11.-Substituted acrylic compounds of the general formula wherein R represents a member of the group consisting of hydrogen and an alkyl group of from 1 to 4 carbon atoms, and R1 represent a member of the group consisting of an alkyl group having from. 1 to 4 carbon atoms.

2. a-Substituted acrylic acids of the general formula wherein R is an alkyl group of from 1 to 4 carbon atoms.

3. tar-Substituted acrylic acid esters of the general formula wherein R and R1 each are alkyl groups of from 1 to 4 carbon atoms.

4. The a-substituted acrylic acid CHz=C-C 0 0H NH-O o 0 0,11, 5. The a-substituted acrylic acid ester CH1=G-G O O CH:

NHOOOC:H

6. The a-substituted acrylic acid ester 0H,: o-o 0 0 CH;

i im-ooocam '7. The c-substituted acrylic acid ester GHz=C-C 0 0 02H;

NH-C 0 0 01H! 8. A polymer of an a-substituted acrylic compound of the general formula CH =COOOR NH-COOR1 wherein R represents a member of the group consisting of hydrogen and an alkyl group of from 1 to 4 atoms, and R1 represents a member of the group consisting of an alkyl group having from 1 to 4 carbon atoms.

9. A polymer of an a-substituted acrylic acid of the general formula capo-o 0 on NH-C 0 o R wherein R is an alkyl group of from 1 to 4 carbon atoms.

10. A polymer of an a-substituted acrylic acid ester of the general formula CH9=G-CO OR NH-COORi wherein R and R1 each are alkyl groups of from 1 to 4 carbon atoms.

11. A copolymer obtained by the polymerization 7 ofiarmixturecomprising a compound of the genera-1 formula;

H2=o0 o o R NH-C o 0 R1 wherein R representsa' member of 'thegroup con-- sisting ofhydrogen and an alkyl group-of from- 1 to 4 carbon atoms; and R1 represents-a member of' the group consisting of an alkyl grouphaving: from 1 to 4 carbon atoms, anda compoundcon taining a polymerizable CH=C group.

12 A'copolymer'obtained by the polymerization of a mixture comprising a compound of"the' -gen'- era formula CH2=GC'O'OR NH-GOTORi V wherein R represents a member ofthegroupconsistingj of hydrogen and an alkyl groupof from- 1' to 4 carbonatoms, and-R1 represents a member of the group consisting of an'alkyl group having from 1 to 4'carbon atoms; and a compound containing a polymerizable CH2=C group.

13. A copolymer-obtained by the polymerization of a mixture comprising a compound of the general formula CH2: 0-0 0 OH NH' coo R wherein R is an alkyl group of from 1'to-4 carbon atoms, and a compound containing a polymerizable CHz=C group.

14. A copolymer obtained by the polymerization of a mixture comprising a compound oft1ie general formula wherein R and R1 each are alkyl groups of from 1 to 4 carbon atoms, and a compound containing a" polymerizable CH2=C group:

15 A copolymerobtained by the polymeriza tion of a mixture comprisinga compoundsoffthegeneral formula NH'G0O"R1 wherein R represnts a member of theagrourr consisting of hydrogen and an alkyl group: of from? 1: to 4; carbon atoms; and R1 represents: a"; member ofthe group'consistingof an alkylqgroupr hayingr from 1 to 4 carbon atoms, and a compound ofthe group consisting of, acrylonitrile, styrene, vinyl acetate and. vinyl chloride.

JOSEPH B; DICKEY. HARRY W. COOVER; JR:

7 REFERENCES: CITED The following references are of record in the file of this patent: i

Rinkes-z Rec. Trav. Chim., 46, 274(192'7). Hoch: Compt. rend., 201, 560-5462 (1935.). 

1. A-SUBSTITUTED ACRYLIC COMPOUNDS OF THE GENERAL FORMULA 